CN1143540A - Process for preparing aromatic hydrocarbon oxidation catalyst - Google Patents
Process for preparing aromatic hydrocarbon oxidation catalyst Download PDFInfo
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- CN1143540A CN1143540A CN 96107093 CN96107093A CN1143540A CN 1143540 A CN1143540 A CN 1143540A CN 96107093 CN96107093 CN 96107093 CN 96107093 A CN96107093 A CN 96107093A CN 1143540 A CN1143540 A CN 1143540A
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- aromatic hydrocarbon
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- phenol
- molecular sieve
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Abstract
A process for preparing arylhydrocarbon oxidizing catalyst is disclosed. Hydrogen peroxide as oxidant is used to prepare phenol by catalytic oxidation of benzene, p-benzendiol by catalyzing phenol, guaiacol by catalytic hydroxylation of anisole, and benzldehyde by catalytic oxidation of styrene. Said catalyst features easy preparation, low cost, high transform rate (over 22%) and selectivity (over 75%) and long service life.
Description
The invention belongs to the technology of preparing of aromatic hydrocarbon oxidation catalyst.
People such as 19th-century Italy Enichem eighties company's T amasso have synthesized the TS-1 molecular sieve of titaniferous, have catalytic oxidation performance.Is benzenediol (this paper is meant the two general designation of catechol and hydroquinones) with hydrogen peroxide for the oxidizer catalytic oxidation of phenol, and conversion ratio reaches 25%.The success of TS-1 molecular sieve catalyst is the example that zeolite molecular sieve is used in catalytic field.But TS-1 molecular sieve synthetic technological condition harshness, the product poor repeatability is difficult to produce, the cost of catalyst higher (more than 400,000 yuan/ton).In view of the situation, we begin to develop oxidation catalyst.Through experiment repeatedly, finished the present invention finally.
The present invention is a kind of aromatic hydrocarbon oxidation catalyst, makees oxidant with hydrogen peroxide, can catalysis benzene oxidation system phenol; The catalysis of phenol preparing benzenediol; Catalysis methyl phenyl ethers anisole hydroxylating system guaiacol; Styrene catalyzed oxidation system phenylacetaldehyde.This catalyst has that preparation is simple, is suitable for industrial production, good repetitiveness, and cost is lower, stable performance, characteristics such as conversion ratio is greater than 22%, and selectivity is greater than 75%, and the life-span is long.
The carrier component of catalyst of the present invention is respectively to contain element silicon or former powder of zeolite molecular sieve siliceous, aluminium element and natural silicon-aluminum containing inorganic mineral powder.For example: the ZSM-5 zeolite of better heat stability, β zeolite and overstable gamma zeolite molecular sieve; A type, X type and y-type zeolite molecular sieve that heat endurance is relatively poor; And kaolin, diatomite, bentonite, gangue and quartzy or the like.
Preparation of catalysts method of the present invention is: above-mentioned inorganic matter carrier is through transition metal ions inorganic acid saline solution such as Fe
3+, Cu
2+, Ga
2+, Ti
3+, Mn
2+, Co
2+, Cr
3+The inorganic acid saline solution of ion, immersion or ion-exchange, one hand over a roasting, two to hand over a roasting; After two friendships, two roasting methods are handled, just become the aromatic hydrocarbon oxidation catalyst of stable performance.
1, infusion method:
Get one of above-mentioned various catalyst carriers and put into the above-mentioned inorganic acid salt aqueous solution soaking that contains a metal ion species respectively, solution concentration is 0.01mol one saturated solution (saturated solution of soaking temperature), soaking temperature is O＜T≤100 ℃, soak time was separated after filtration greater than 1 minute, solid phase just is catalyst of the present invention through oven dry.
2, ion-exchange:
One of above-mentioned various catalyst carriers are dropped in the above-mentioned inorganic acid saline solution that contains a metal ion species respectively, stir.Solution concentration is 0.01mol one saturated solution (saturated solution under the treatment temperature), treatment temperature 0＜T≤100 ℃, mixing time is that 1 minute＜T＜48 hour solution usage be a minimum with the energy submergence, handles after isolated by filtration is dried and is catalyst of the present invention.This method is saved time than infusion method and evenly.
3, one hand over a roasting method:
Through the catalyst of ion-exchange (2) gained or through the catalyst of infusion method (1) gained, be 200-900 ℃ of roasting through excess temperature, reach temperature after the constant time greater than 1 hour; Just be catalyst of the present invention.Long through the calcined catalyst life-span.
4, two hand over a roasting method:
Carrier-zeolite molecular sieve separates and soaks after the oven dry once for secondary soaks again through once soaking the back, or separates oven dry through primary ions exchange back and carry out primary ions again and be exchanged for the secondary exchange, and the gained catalyst is through the condition bakes to burn the article of (3) together.
5, two hand over two roasting methods:
The molecular sieve condition is the same described through once repeating promptly again through soaking or exchange-separation oven dry-calcination process after immersion or the exchange-separation oven dry-roasting.Make catalyst.This catalyst ion exchange is thorough, stable.
Embodiment 1
The former powder of ZSM-5 zeolite molecular sieve passes through FeCl
3Immersion or the exchange result that handles rear catalyst and catalysis of phenol preparing benzenediol as follows:
| Support modification modification method of modifying temperature-time | The hydroxylating condition | Phenol conversion | Selectivity |
| Time-temperature phenol/H 2O 2Phenol/catalyst molar ratio weight ratio | |||
| 0.3mol 30 hours FeCl of room temperature 3Solution soaks | 4 hours 60 ℃ 3: 1 10: 1 | ????23％ | ????80.0％ |
| 0.3mol FeCl 3100 ℃ of solution exchanges 1 hour | 4 hours 60 ℃ 3: 1 10: 1 | ????24％ | ????85.0％ |
Embodiment 2:
1.0molGaSO
4Solution is as follows to the result of the former powder modification of carrier y-type zeolite silks catalyst and catalysis of phenol hydroxylating:
| Support modification modification method of modifying temperature-time | The hydroxylating condition | Phenol conversion | Selectivity |
| Time-temperature phenol/H 2O 2Phenol/catalyst molar ratio weight ratio | |||
| 1.0mol 100 ℃ of 1 hour GaSO 436 hours GaSO of exchange 1.0mol room temperature 4Soak | 4 hours 60 ℃ 3: 1 10: 14 hours 60 ℃ 3: 1 10: 1 | ????24％ ????22％ | ????81.0％ ????84.5％ |
Embodiment 3
Adopt 0.3molCuSO
4The result of the natural pit coal spoil of solution dipping carrier powder catalysis of phenol hydroxylating is as follows:
| Support modification modification method of modifying temperature-time | The hydroxylating condition | Phenol conversion | Selectivity |
| Time-temperature phenol/H 2O 2Phenol/catalyst molar ratio weight ratio | |||
| 0.3mol 20 hours CuSO of room temperature 4Solution soaks | 2 hours 80 ℃ 3: 1 10: 1 | ????24％ | ??75％ |
Embodiment 4
The Fe-ZSM-5 catalyst methyl phenyl ethers anisole hydroxylating system guaiacol of embodiment 1, its result is as follows:
The Fe-ZMS-5 catalyst styrene oxide system phenylacetaldehyde of embodiment 5 usefulness embodiment 1, the result is as follows:
| Catalyst | Methyl phenyl ethers anisole/H 2O 2Methyl phenyl ethers anisole/catalyst temperature time mol ratio weight ratio | The conversion ratio selectivity |
| Fe-ZSM-5 | 1.5: 1.0 40: 1 70 ℃ 6 hours | ?40％??????95％ |
| Catalyst | Methyl phenyl ethers anisole/H 2O 2Methyl phenyl ethers anisole/catalyst temperature time mol ratio weight ratio | The conversion ratio selectivity |
| Fe-ZSM-5 | 1.5: 1 20: 1 65 ℃ 6 hours | ?45.0％?????75％ |
Claims (2)
1, the present invention is a kind of technology of preparing of aromatic hydrocarbon oxidation catalyst, and its characteristic is: the carrier component of catalyst is former powder of zeolite molecular sieve siliceous or siliceous, aluminium element and natural silicon-aluminum containing inorganic mineral powder.Carrier hands over a roasting, two to hand over a roasting, two to hand over two roastings to handle through transition metal ions inorganic strong acid salt aqueous solution soaking or exchange,, treatment conditions are that solution concentration is the 0.01mol-saturated solution, treatment temperature: 0＜T≤100 ℃, sintering temperature: 200-900 ℃, immersion or swap time were greater than 1 minute.Just become the aromatic hydrocarbon oxidation catalyst of stable performance.Catalyst of the present invention is to be oxidant with hydrogen peroxide, can catalysis benzene oxidation system phenol, the oxidation phenol preparing benzenediol, and catalysis methyl phenyl ethers anisole hydroxylating system guaiacol, styrene catalyzed oxidation system phenylacetaldehyde.Its conversion ratio is greater than 22%, and selectivity is greater than 75%.
2, as right the technology of preparing of 1 described aromatic hydrocarbon oxidation catalyst, its characteristic is the carrier component of catalyst, is respectively: the ZSM-5 zeolite, the β zeolite, overstable gamma zeolite, molecular sieve, A type, X type, y-type zeolite molecular sieve, and kaolin, diatomite, bentonite, gangue.Transition metal ions is respectively Fe
3+, Cu
2+, Ga
2+, Ti
3+, Mn
2+, Co
2+, Cr
3+
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96107093A CN1060970C (en) | 1996-07-18 | 1996-07-18 | Process for preparing aromatic hydrocarbon oxidation catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96107093A CN1060970C (en) | 1996-07-18 | 1996-07-18 | Process for preparing aromatic hydrocarbon oxidation catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1143540A true CN1143540A (en) | 1997-02-26 |
| CN1060970C CN1060970C (en) | 2001-01-24 |
Family
ID=5119532
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96107093A Expired - Fee Related CN1060970C (en) | 1996-07-18 | 1996-07-18 | Process for preparing aromatic hydrocarbon oxidation catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1060970C (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1104405C (en) * | 2000-10-11 | 2003-04-02 | 吉林大学 | Tar-free catalytic oxidation of arene utilizing coupling reaction |
| CN100443172C (en) * | 2002-09-11 | 2008-12-17 | 中国科学院大连化学物理研究所 | Accelerating agent and its application in synthesizing carbolic acid using benzene and hydrogen dioxide |
| CN101468801B (en) * | 2007-12-27 | 2011-05-18 | 中国石油化工股份有限公司 | Method for preparing Y type molecular sieve containing mesoporous |
| CN102861570A (en) * | 2011-07-07 | 2013-01-09 | 北京三聚创洁科技发展有限公司 | Composite type coal tar hydrogenation catalyst and preparation method thereof |
| US20130324761A1 (en) * | 2011-02-02 | 2013-12-05 | University College Cardiff Consulltants Limited | Hydrocarbons selective oxidation with heterogeneous catalysts |
| CN106588577A (en) * | 2015-10-19 | 2017-04-26 | 江苏福瑞生物医药有限公司 | Pentafluorophenol synthesis method |
| CN112691696A (en) * | 2020-12-23 | 2021-04-23 | 华电电力科学研究院有限公司 | Preparation method of aromatization catalyst taking coal gangue as raw material |
| CN115504868A (en) * | 2021-06-23 | 2022-12-23 | 中国石油化工股份有限公司 | Method and device for producing guaiacol from phenol |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT964049B (en) * | 1972-08-18 | 1974-01-21 | Brichima Spa | PROCESS FOR THE PREPARATION OF DIPHENOLS |
| US4578521A (en) * | 1985-02-04 | 1986-03-25 | Mobil Oil Corporation | Shape-selective catalytic oxidation of phenol |
| FR2630734B1 (en) * | 1988-05-02 | 1990-07-27 | Rhone Poulenc Chimie | PROCESS FOR THE PREPARATION OF DIHYDROXYBENZENES |
| FR2693457B1 (en) * | 1992-07-10 | 1994-09-02 | Rhone Poulenc Chimie | Process for the hydroxylation of phenolic compounds. |
| CN1050537C (en) * | 1994-12-28 | 2000-03-22 | 中国科学院长春应用化学研究所 | Phenol hydroxylated synthetic o-dihydroxybenzene (catechol) and P-benzenediol (hydroquinone) catalyzer |
-
1996
- 1996-07-18 CN CN96107093A patent/CN1060970C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1104405C (en) * | 2000-10-11 | 2003-04-02 | 吉林大学 | Tar-free catalytic oxidation of arene utilizing coupling reaction |
| CN100443172C (en) * | 2002-09-11 | 2008-12-17 | 中国科学院大连化学物理研究所 | Accelerating agent and its application in synthesizing carbolic acid using benzene and hydrogen dioxide |
| CN101468801B (en) * | 2007-12-27 | 2011-05-18 | 中国石油化工股份有限公司 | Method for preparing Y type molecular sieve containing mesoporous |
| US20130324761A1 (en) * | 2011-02-02 | 2013-12-05 | University College Cardiff Consulltants Limited | Hydrocarbons selective oxidation with heterogeneous catalysts |
| CN102861570A (en) * | 2011-07-07 | 2013-01-09 | 北京三聚创洁科技发展有限公司 | Composite type coal tar hydrogenation catalyst and preparation method thereof |
| CN102861570B (en) * | 2011-07-07 | 2015-12-02 | 北京宝塔三聚能源科技有限公司 | A kind of compound coal tar hydrogenation catalyst and preparation method thereof |
| CN106588577A (en) * | 2015-10-19 | 2017-04-26 | 江苏福瑞生物医药有限公司 | Pentafluorophenol synthesis method |
| CN106588577B (en) * | 2015-10-19 | 2019-08-06 | 江苏福瑞康泰药业有限公司 | The synthetic method of Pentafluorophenol |
| CN112691696A (en) * | 2020-12-23 | 2021-04-23 | 华电电力科学研究院有限公司 | Preparation method of aromatization catalyst taking coal gangue as raw material |
| CN115504868A (en) * | 2021-06-23 | 2022-12-23 | 中国石油化工股份有限公司 | Method and device for producing guaiacol from phenol |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1060970C (en) | 2001-01-24 |
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